CN102816586B - Demetalization method for crude oil - Google Patents
Demetalization method for crude oil Download PDFInfo
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- CN102816586B CN102816586B CN201110153198.3A CN201110153198A CN102816586B CN 102816586 B CN102816586 B CN 102816586B CN 201110153198 A CN201110153198 A CN 201110153198A CN 102816586 B CN102816586 B CN 102816586B
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Abstract
The invention relates to a demetalization method for crude oil. The method includes that (1) phosphate ester, oil soluble peroxide and the crude oil are mixed and react for a period of time>=30 min at the temperature of 80-180 DEG C, the mass of the crude oil serves as a standard, use amount of phosphate ester is 80-10000 mu g/g, use amount of oil soluble peroxide is 5-2000 mu g/g, and nickel content and/or vanadium content >=5 mu g/g; and (2) the crude oil obtained in the step (1) is processed through electro-desalting processing. The method has the advantages of being high in demetalization rate, small in chemical agent use amount, mild in reaction conditions, simple in process and devices and the like and is especially suitable for crude oil with high content of nickel and vanadium.
Description
Technical field
The invention belongs to the process for purification of hydrocarbon ils.Specifically, the present invention relates to a kind of demetallated method of crude oil.
Background technology
Along with the widespread use of Deep mining and the tertiary oil recovery technology of crude oil, a large amount of heavy crude are exploited out, and the metal content of these crude oil is continuous ascendant trend as calcium, magnesium, sodium, iron, nickel, vanadium, copper etc.In the metallic impurity of crude oil, the content of nickel and vanadium is higher and mainly with metalloporphyrin complex and complicated oil soluble macromolecular compound form existence, electric desalting process is difficult to them to remove.Metallic impurity in crude oil can have a negative impact to the secondary processing process of crude oil, cause poisoning of catalyst, activity decreased, agent consumption to increase, and wherein the harm of nickel and vanadium is the most outstanding.
Metallic compound in crude oil at high temperature decomposes, and the metal producing after decomposing is deposited on catalyst surface, thereby changes the character of catalyzer.Metallic nickel major sedimentary, on the surface of support of the catalyst, shows strong dehydrogenation, and the productive rate of hydrogen and coke is increased, and changes selectivity of catalyst and catalyst activity is not produced to obvious impact.Vanadium metal initial deposition is at catalyst surface, but can move to gradually on molecular sieve, due to the raising of sodium content, vanadium can form with it low melting point eutectic, and molecular sieve structure is damaged, and catalyst surface area reduces, activity decreased, and vanadium is irreversible to the toxication of catalyzer.In heavy-oil hydrogenation treating processes, because demetalization reaction is the most easily carried out, the metal removing is deposited on catalyst surface with the form of sulfide immediately, blocking catalyst duct, thus cause poisoning of catalyst.
At present, the industrial method that removes metallic impurity in crude oil is mainly hydrogenation method and solvent deasphalting method.Hydrodemetallation (HDM) can reduce nickel, the vanadium in stock oil effectively, but is not suitable for the raw material that metal content is high, and exists plant investment huge, and spent catalyst is difficult to the shortcoming of regeneration; Solvent deasphalting method is only applicable to remove the crude oil that asphalt content is high, and can only remove nickel, vanadium in pitch, and investment is large, and process cost is high.People are exploring the demetallated novel method of crude oil always, as chelating separation, solvent extraction, electrolytic reduction, thermo-cracking, absorption method etc.These novel methods are owing to having the problems such as metal removal efficiency is low, running cost is high, still unrealized industrialization so far.
Start the research of chemical method nickel removal, vanadium abroad from the 1950's.Chemical method nickel removal, vanadium add chemical agent exactly in stock oil, make it with stock oil in nickel and vanadium compound react, then reaction product is separated, thereby reaches the object of nickel removal, vanadium.US4645589 discloses a kind of demetallated method of crude oil, and the aqueous solution of P contained compound is reacted in special equipment with stock oil, makes metallic nickel, vanadium be extracted into water, thereby then aqueous phase separation is removed to nickel, vanadium.In the method, medicament with crude quality than 0.01～0.04, water with crude quality than 0.2～1,80～200 ℃ of temperature of reaction, duration of contact 5～60min, nickel, vanadium decreasing ratio can reach respectively 39% and 41%.US4529503 discloses a kind of demetallated method of hydrocarbonaceous stream, element phosphor or P contained compound (as phosphorous acid) are mixed with containing metal hydrocarbon ils, under 300～450 ℃, high pressure and hydrogen condition, react, the metal such as nickel, vanadium in element phosphor or P contained compound and hydrocarbon ils is formed and be insoluble to oily compound, then adopt the means such as centrifugal, sedimentation or filtration to isolate reaction product nickeliferous, vanadium.
In sum, the deficiencies such as existing chemical method demetalization technology exists that consumption of chemical agent is large, complex process, equipment requirements are high, severe reaction conditions, and its demetallization per also needs further to be improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of demetallated method of crude oil.The method has the features such as demetallization per is high, consumption of chemical agent is little, reaction conditions is gentle, Processes and apparatus is simple, and it is specially adapted to nickel, crude oil that content of vanadium is high.
A kind of demetallated method of crude oil, comprising:
(1) phosphorous acid ester, oil soluble superoxide are mixed with crude oil, reaction >=30min at 80～180 ℃, take the quality of crude oil as benchmark, the consumption of phosphorous acid ester is 80～10000 μ g/g, the consumption of oil soluble superoxide is 5～2000 μ g/g, the nickel content in described crude oil and/or content of vanadium >=5 μ g/g;
(2) crude oil that adopts technology of electric de-salting treatment step (1) to obtain.
Nickel content in described crude oil and/or content of vanadium preferably >=20 μ g/g.
Take the quality of crude oil as benchmark, the consumption of phosphorous acid ester is preferably 400～5000 μ g/g.
Take the quality of crude oil as benchmark, the consumption of oil soluble superoxide is preferably 25～1000 μ g/g.
Described phosphorous acid ester can be selected from one or more in dimethylphosphite, trimethyl phosphite, diethyl phosphite, triethyl-phosphite, diphenyl phosphite and diisopropyl phosphite, is preferably dimethylphosphite and/or trimethyl phosphite.
Described oil soluble superoxide can be selected from hydrogen peroxide sec.-propyl, t-butyl hydroperoxide, di-t-butyl peroxide, 1,1,3,3-tetramethyl butyl hydroperoxide, peroxidation be two-and (1-hydroxyl hexanaphthene), 1,1-pair-(tert-butyl peroxide) hexanaphthene, 2,2-pair-(tert-butyl peroxide) propane, 2,2-is two-one or more in (tert-butyl peroxide) butane, dicumyl peroxide, dicumyl peroxide, tert-butyl peroxide benzene and hydrogen peroxide di-t-butyl isopropyl benzene, be preferably tert-butyl peroxide benzene.
The temperature of reaction of step (1) is preferably 100～140 ℃.
The reaction times of step (1) is preferably 30～240min.
In step (1), can adopt one or more the combination in mechanical stirring, mixing valve, static mixer that phosphorous acid ester, oil soluble superoxide are mixed with crude oil.
In step (2), can adopt conventional technology of electric de-salting, its operational condition is generally: take the quality of crude oil as benchmark, the consumption of emulsion splitter is 10～100 μ g/g; Take the quality of crude oil as 100%, the consumption of water filling is 4%～10%; Temperature is 110～150 ℃; Strength of electric field is 400～2000V/cm; The residence time is 20～120min.
The present invention has no particular limits emulsion splitter, can select conventional emulsion splitter, as polyethers emulsion splitter.Described polyethers emulsion splitter can be polyox-yethylene-polyoxypropylene block copolymer, as the polyox-yethylene-polyoxypropylene block copolymer take fatty alcohol as initiator, polyox-yethylene-polyoxypropylene block copolymer take amine as initiator, take resol or phenol-amine resin as the polyox-yethylene-polyoxypropylene block copolymer of initiator or the polyox-yethylene-polyoxypropylene block copolymer take tolylene diisocyanate as chainextender.The number-average molecular weight of polyox-yethylene-polyoxypropylene block copolymer can be 1000～50000.
Reaction in the present invention and electric desalting process preferably adopt continuous mode to carry out.
The deficiencies such as existing chemical method demetalization technology exists that consumption of chemical agent is large, complex process, equipment requirements are high, severe reaction conditions, and its demetallization per also needs further to be improved.The present invention adopts phosphorous acid ester and oil soluble superoxide to react with nickel, vanadium compound in crude oil, make nickel, vanadium compound be converted into precipitation, hydrophilic or water miscible compound, then by technology of electric de-salting, reaction product is separated, thereby reach the demetallated object of crude oil.
Compared with prior art, the present invention has the following advantages:
1. nickel of the present invention, vanadium decreasing ratio are high.Adopt method of the present invention, nickel decreasing ratio can reach more than 60%, and vanadium decreasing ratio can reach more than 80%, and total decreasing ratio of calcium, magnesium, iron can reach more than 80%.
2. temperature of reaction of the present invention and pressure are lower, and consumption of chemical agent is less.
3. equipment of the present invention is simple, technique is reasonable, easy and simple to handle.The present invention only need increase a set of demetalization conversion unit before the existing electric desalting apparatus in refinery, demetalization reaction process can with the same heat exchange process of crude oil electric desalting process using, do not need to increase any cold exchange device.Because temperature of reaction of the present invention is suitable with electric desalting temperature, therefore reacted crude oil can directly enter refinery's electric desalting apparatus and carries out desalination, dehydration, nickel, vanadium is removed simultaneously.
Embodiment
Embodiment 1
Certain domestic crude oil, metal content: nickel 33.5 μ g/g, vanadium 222.4 μ g/g, calcium 17.5 μ g/g, magnesium 1.6 μ g/g, iron 6.8 μ g/g.
In crude oil, add the dimethylphosphite of 1700 μ g/g, the tert-butyl peroxide benzene of 300 μ g/g, at 130 ℃, be uniformly mixed, reaction 180min.Then to the polyether demulsification agent ST-14 (purchased from Binzhou, Shandong Chemical Group) that adds 100 μ g/g in crude oil, the water of crude quality 6%, after emulsion splitter, water are fully mixed with crude oil, the 80min that dewaters at 140 ℃, in the electric field of 1500V/cm, has obtained removing the oil sample of metal.With the metal content of inductively coupled plasma emission spectrometry oil sample, the results are shown in Table 1.
Table 1
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 11.5 | 42.2 | 3.0 | 0.3 | 1.6 |
| Metal removal rate/% | 65.7 | 81.0 | 82.9 | 81.3 | 76.5 |
Embodiment 2
Test crude oil is identical with embodiment 1.Adopt the method identical with embodiment 1 to remove the metal in crude oil, different, the consumption of dimethylphosphite and tert-butyl peroxide benzene is 15% of embodiment 1 consumption.Experimental result is in table 2.
Table 2
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 24.0 | 118.8 | 8.7 | 0.5 | 3.2 |
| Metal removal rate/% | 28.4 | 46.6 | 50.3 | 68.8 | 52.9 |
Embodiment 3
Test crude oil is identical with embodiment 1.Adopt the method identical with embodiment 1 to remove the metal in crude oil, different, the consumption of dimethylphosphite is 1940 μ g/g, and the consumption of tert-butyl peroxide benzene is 60 μ g/g.Test-results is in table 3.
Table 3
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 17.2 | 78.3 | 2.9 | 0.4 | 1.8 |
| Metal removal rate/% | 48.7 | 64.8 | 83.4 | 75.0 | 73.5 |
Comparative example 1
Test crude oil is identical with embodiment 1.Adopt the method identical with embodiment 1 to remove the metal in crude oil, different, the consumption of dimethylphosphite is 2000 μ g/g, does not use tert-butyl peroxide benzene.Test-results is in Table 4a.
Table 4a
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 19.5 | 92.1 | 2.8 | 0.3 | 1.6 |
| Metal removal rate/% | 41.8 | 58.6 | 84.0 | 81.3 | 76.5 |
Embodiment 4
Test crude oil is identical with embodiment 1.In crude oil, add the diethyl phosphite of 2500 μ g/g, the diphenyl phosphite of 2000 μ g/g, the hyperis of 500 μ g/g, under 120 ℃ of conditions, be uniformly mixed, reaction 180min.Then add the polyether demulsification agent ST-14 of 100 μ g/g, the water of crude quality 8%, after emulsion splitter, water are fully mixed with crude oil, the 60min that dewaters at 140 ℃, in the electric field of 1800V/cm, has obtained removing the oil sample of metal.With the metal content of inductively coupled plasma emission spectrometry oil sample, the results are shown in Table 4.
Table 4
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 15.4 | 89.4 | 3.1 | 0.5 | 1.9 |
| Metal removal rate/% | 54.0 | 59.8 | 82.3 | 68.8 | 72.1 |
Embodiment 5
Certain imported crude oil, metal content: nickel 13.4 μ g/g, vanadium 26.2 μ g/g, calcium 25.4 μ g/g, magnesium 2.8 μ g/g, iron 13.9 μ g/g.
To add in crude oil 800 μ g/g triethyl-phosphite, 200 μ g/g 1,1-is two-(tert-butyl peroxide) hexanaphthene, is uniformly mixed reaction 60min at 130 ℃.Then add the polyether demulsification agent ST-14 of 20 μ g/g, the water of crude quality 5%, after emulsion splitter, water are fully mixed with crude oil, the 40min that dewaters at 110 ℃, in the electric field of 600V/cm, has obtained removing the oil sample of metal.With the metal content of inductively coupled plasma emission spectrometry oil sample, the results are shown in Table 5.
Table 5
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 6.9 | 10.2 | 7.8 | 1.0 | 5.6 |
| Metal removal rate/% | 48.5 | 61.1 | 69.3 | 64.3 | 59.7 |
Embodiment 6
Test crude oil is identical with embodiment 5.In crude oil, add the trimethyl phosphite of 4000 μ g/g, the diisopropyl phosphite of 750 μ g/g, the di-t-butyl peroxide of 300 μ g/g, the dicumyl peroxide of 150 μ g/g, at 140 ℃, be uniformly mixed, reaction 150min.Then add the polyether demulsification agent ST-14 of 60 μ g/g, the water of crude quality 10%, after emulsion splitter, water are fully mixed with crude oil, the 100min that dewaters at 140 ℃, in the electric field of 1400V/cm, has obtained removing the oil sample of metal.With the metal content of inductively coupled plasma emission spectrometry oil sample, the results are shown in Table 6.
Table 6
| Project | Nickel | Vanadium | Calcium | Magnesium | Iron |
| Metal content/(μ g/g) after de- | 4.5 | 5.0 | 4.9 | 0.9 | 3.4 |
| Metal removal rate/% | 66.4 | 80.9 | 80.7 | 67.9 | 75.5 |
Claims (11)
1. the demetallated method of crude oil, comprising:
(1) phosphorous acid ester, oil soluble superoxide are mixed with crude oil, reaction >=30min at 80～180 ℃, take the quality of crude oil as benchmark, the consumption of phosphorous acid ester is 80～10000 μ g/g, the consumption of oil soluble superoxide is 5～2000 μ g/g, the nickel content in described crude oil and/or content of vanadium >=5 μ g/g;
(2) crude oil that adopts technology of electric de-salting treatment step (1) to obtain; The processing condition of electric desalting are: take the quality of crude oil as benchmark, the consumption of emulsion splitter is 10～100 μ g/g; Take the quality of crude oil as 100%, the consumption of water is 4%～10%; Temperature is 110～150 ℃; Strength of electric field is 400～2000V/cm; The residence time is 20～120min.
2. in accordance with the method for claim 1, it is characterized in that the nickel content in described crude oil and/or content of vanadium >=20 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, take the quality of crude oil as benchmark, the consumption of phosphorous acid ester is 400～5000 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, take the quality of crude oil as benchmark, the consumption of oil soluble superoxide is 25～1000 μ g/g.
5. in accordance with the method for claim 1, it is characterized in that, described phosphorous acid ester is selected from one or more in dimethylphosphite, trimethyl phosphite, diethyl phosphite, triethyl-phosphite, diphenyl phosphite and diisopropyl phosphite.
6. in accordance with the method for claim 1, it is characterized in that, described oil soluble superoxide is selected from hydrogen peroxide sec.-propyl, t-butyl hydroperoxide, di-t-butyl peroxide, 1, 1, 3, 3-tetramethyl butyl hydroperoxide, peroxidation is two-and (1-hydroxyl hexanaphthene), 1, 1-pair-(tert-butyl peroxide) hexanaphthene, 2, 2-pair-(tert-butyl peroxide) propane, 2, 2-pair-(tert-butyl peroxide) butane, dicumyl peroxide, dicumyl peroxide, one or more in tert-butyl peroxide benzene and hydrogen peroxide di-t-butyl isopropyl benzene.
7. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of step (1) is 100～140 ℃.
8. in accordance with the method for claim 1, it is characterized in that, the reaction times of step (1) is 30～240min.
9. in accordance with the method for claim 1, it is characterized in that, in step (1), the combination of one or more in employing mechanical stirring, mixing valve, static mixer mixes phosphorous acid ester, oil soluble superoxide with crude oil.
10. in accordance with the method for claim 1, it is characterized in that, described emulsion splitter is that fatty alcohol is the polyox-yethylene-polyoxypropylene block copolymer of initiator, polyox-yethylene-polyoxypropylene block copolymer take amine as initiator, take resol or phenol-amine resin as the polyox-yethylene-polyoxypropylene block copolymer of initiator or the polyox-yethylene-polyoxypropylene block copolymer take tolylene diisocyanate as chainextender.
11. in accordance with the method for claim 10, it is characterized in that, the number-average molecular weight of described polyox-yethylene-polyoxypropylene block copolymer is 1000～50000.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614081A (en) * | 1995-06-12 | 1997-03-25 | Betzdearborn Inc. | Methods for inhibiting fouling in hydrocarbons |
| CN101469279A (en) * | 2007-12-24 | 2009-07-01 | 中国石油化工股份有限公司 | Method for removing nickel and vanadium in hydrocarbon raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614081A (en) * | 1995-06-12 | 1997-03-25 | Betzdearborn Inc. | Methods for inhibiting fouling in hydrocarbons |
| CN101469279A (en) * | 2007-12-24 | 2009-07-01 | 中国石油化工股份有限公司 | Method for removing nickel and vanadium in hydrocarbon raw material |
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